[3-(5-Hy­droxy-5H-dibenzo[a,d]cyclo­hepten-5-yl)prop­yl]dimethyl­ammonium 3-carboxyprop-2-enoate

Jerry P Jasinski; James A Golen; M S Siddegowda; H S Yathirajan; B Narayana

doi:10.1107/S1600536811036257

. 2011 Sep 14;67(Pt 10):o2600–o2601. doi: 10.1107/S1600536811036257

[3-(5-Hydroxy-5H-dibenzo[a,d]cyclohepten-5-yl)propyl]dimethylammonium 3-carboxyprop-2-enoate

Jerry P Jasinski ^a,^*, James A Golen ^a, M S Siddegowda ^b, H S Yathirajan ^b, B Narayana ^c

PMCID: PMC3201273 PMID: 22058751

Abstract

In the cation of the title salt, C₂₀H₂₄NO⁺·C₄H₃O₄ ⁻, the N atom in the dimethylammonium group is protonated. The dihedral angle between the mean planes of the two six-membered rings fused to the cyclohepten-5-yl ring is 54.4 (1)°. An intramolecular O—H⋯O hydrogen bond occurs in the anion. The crystal packing is stabilized by intermolecular O—H⋯O and N—H⋯(O,O) hydrogen bonds and weak C—H⋯O interactions, forming a two-dimensional network.

Related literature

The title compound is used in the preparation of cyclobenzaprine (systematic name: 3-(5H-dibenzo[a,d]cyclohepten-5-ylidene)-N,N-dimethyl-1-propanamine), a muscle relaxant used to relieve skeletal muscle spasms and associated pain in acute musculoskeletal conditions. For its structural relationships to first-generation tricyclic antidepressants, see: Commissiong et al. (1981 ▶); Katz & Dube (1988 ▶); Cimolai (2009 ▶). For related structures, see: Bindya et al. (2007 ▶); Jasinski, Pek et al. (2010 ▶); Jasinski, Butcher et al. (2010 ▶); Fun et al. (2011 ▶); Siddegowda et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₀H₂₄NO⁺·C₄H₃O₄ ⁻
M _r = 409.47
Monoclinic,
a = 9.2115 (2) Å
b = 11.5840 (2) Å
c = 10.4640 (2) Å
β = 101.591 (2)°
V = 1093.80 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 K
0.40 × 0.22 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.966, T _max = 0.983
9674 measured reflections
2834 independent reflections
2683 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.093
S = 1.04
2834 reflections
282 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036257/bt5634sup1.cif

e-67-o2600-sup1.cif^{(30.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036257/bt5634Isup2.hkl

e-67-o2600-Isup2.hkl^{(139.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036257/bt5634Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O3ⁱ	0.83 (2)	1.95 (2)	2.770 (2)	173 (2)
O2—H2O⋯O4	0.89 (2)	1.56 (2)	2.442 (2)	171 (4)
N1—H1N⋯O5	0.88 (2)	1.80 (2)	2.6797 (19)	172 (2)
N1—H1N⋯O4	0.88 (2)	2.69 (2)	3.340 (2)	131 (2)
C16—H16B⋯O3ⁱ	0.99	2.63	3.267 (3)	122
C19—H19A⋯O3ⁱⁱ	0.98	2.55	3.452 (3)	154
C20—H20A⋯O3ⁱⁱ	0.98	2.94	3.781 (4)	144
C9—H9A⋯O4ⁱⁱⁱ	0.95	2.82	3.675 (2)	151
C12—H12A⋯O4^iv	0.95	2.62	3.460 (3)	148
C17—H17A⋯O5^v	0.99	2.92	3.865 (2)	159
C20—H20B⋯O5^v	0.98	2.39	3.296 (3)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

MSS thanks UoM for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

The title compound is used for the preparation of cyclobenzaprine. Cyclobenzaprine (Systematic iupac name: 3-(5H-dibenzo[a,d]cyclohepten-5- ylidene)-N,N-dimethyl-1-propanamine) is a muscle relaxant used to relieve skeletal muscle spasms and associated pain in acute musculoskeletal conditions. Cyclobenzaprine has been considered structurally related to the first-generation tricyclic antidepressants (Commissiong et al., 1981; Katz & Dube, 1988; Cimolai, 2009). The crystal structures of amitriptylinium picrate (Bindya et al., 2007), 4-(4-chlorophenyl)-4-hydroxypiperidinium maleate maleic acid solvate (Jasinski, Pek et al., 2010), trimipraminium maleate (Jasinski, Butcher et al., 2010), cyclobenzaprinium salicylate (Fun et al., 2011) and cyclobenzaprinium chloride (Siddegowda et al., 2011) have been reported. In view of the importance of 3-(5-hydroxy-5H-dibenzo[a,d] cyclohepten-5-yl)-propyl]-dimethylammonium maleate, this paper reports the crystal structure of the title salt, (I), C₂₀H₂₄NO⁺.C₄H₃O₄^-.

In the cation of the title salt, C₂₀H₂₄NO⁺.C₄H₃O₄^-, the N atom in the dimethylammonium group is protonated (Fig 1). The dihedral angle between the mean planes of the two benzene rings fused to the seven-membered cyclohepten-5-yl ring is 54.4 (1)°. Crystal packing is stabilized by O—H···O, N—H···O intermolecular hydrogen bonds, N—H···O intramolecular bonds and weak C—H···O intermolecular interactions (Table 1) forming a 2-D network (Fig. 2).

Experimental

3-(5-Hydroxy-5H-dibenzo[a,d]cyclohepten-5-yl)-propyl]-dimethylamine (2.0 g, 0.0068 mol) and maleic acid (0.788 g, 0.0068 mol) were dissolved in 10 ml of ethyl acetate taken in a 50 ml round bottomed flask. The reaction mixture was heated to 323-333 K with constant stirring for 30 min. The product formed was filtered, dried and recrystallized from methanol (m.p.: 419-421 K).